Multi-sensor optical device for detecting chemical species and manufacturing method thereof

ABSTRACT

An optical device for detecting a first chemical species and a second chemical species contained in a specimen, which includes: a first optical sensor, which may be optically coupled to an optical source through the specimen and is sensitive to radiation having a wavelength comprised in a first range of wavelengths; and a second optical sensor, which may be optically coupled to the optical source through the specimen and is sensitive to radiation having a wavelength comprised in a second range of wavelengths, different from the first range of wavelengths.

BACKGROUND Technical Field

The present disclosure relates to a multi-sensor optical device fordetecting chemical species, as well as to the manufacturing methodthereof.

Description of the Related Art

As is known, in different fields of application one can detect one ormore chemical species and then determine the correspondingconcentrations of these chemical species. For instance, in themotor-industry sector, one can determine the concentrations, in anexhaust gas, of chemical species that are generated in the course of thethermal reactions that take place within an engine.

Once again with reference to the motor-industry sector, it is knownthat, following upon a combustion reaction that occurs between the fueland the air, water (H₂O), carbon dioxide (CO₂), carbon monoxide (CO),sulphur oxides (SO_(x)), nitrogen oxides (NO_(x)), hydrocarbons (HC) andparticulate matter (PM) are generated. In addition, nitrogen oxidesinclude nitrogen monoxide (NO), nitrogen dioxide (NO₂), and dinitrogenoxide (N₂O).

Since the chemical species resulting from a combustion reaction concursignificantly in pollution, the control of the levels of emission ofthese chemical species proves to be of particular importance.Consequently, various types of sensors have been developed over time,referred to in general as burnt-gas sensors. For instance, differenttypes of nitrogen-oxide sensors are known, which are commonly employedwithin closed control loops that are designed to control the combustionprocess.

Since the aforementioned burnt-gas sensors usually operate in extremeenvironmental conditions, they are characterized not only by highsensitivity and speeds of response, but also by a considerableresistance to high temperatures, as well as to corrosive chemicalagents. For this reason, known sensors are of silicon carbide (SiC), asdescribed, for example, in the patent application no. DE20051033639. Inthis patent application a sensor is described including a sensing regionof porous material, coated with a functional layer, capable of reactingwith the chemical species to be analyzed; the reaction involves adetectable variation of the concentration of the carriers within thefunctional layer.

In general, burnt-gas sensors based upon the variation, following uponabsorption of a chemical species by a constitutive element thereof, ofan electrical characteristic of this element are characterized by lowcosts and by a certain simplicity of construction; however, they arelikewise characterized by a not particularly high sensitivity, as wellas, at times, by a low selectivity in regard to the chemical speciesabsorbed. In addition, these sensors are far from suited to operating inthe presence of corrosive chemical agents.

Commercial products are likewise known of the type described in thedocument available athttp://www.baytec-inc.com/pdf/defor-extractive-analyzer.pdf. Illustratedin this document is a gas analyzer including a source of UV radiationand two optical detectors. Further, the analyzer enables detection ofmore than one chemical species, thanks to the use of a motor-drivenmobile element, constrained to which is an optical filter so that theoptical filter may be coupled to one of the optical detectors in acontrolled way. Even though this system is characterized by a highaccuracy, it may not be integrated; thus, it presents large overalldimensions and a high complexity. Consequently, this system is mainlysuited for laboratory tests.

BRIEF SUMMARY

According to the present disclosure, a device for detecting chemicalspecies and a manufacturing method thereof are consequently provided.One embodiment of the present disclosure is directed to an opticaldevice that includes an optical source, a first optical sensorconfigured to be optically coupled to the optical source through aspecimen, the specimen having a first chemical species and a secondchemical species, the first optical sensor being sensitive to radiationhaving a wavelength in a first range of wavelengths, and a secondoptical sensor configured to be optically coupled to the optical sourcethrough the specimen, the second optical sensor being sensitive toradiation having a wavelength in a second range of wavelengths,different from the first range of wavelengths.

BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS

For a better understanding of the present disclosure, preferredembodiments thereof are now described, purely by way of non-limitingexample and with reference to the attached drawings, wherein:

FIG. 1 shows a block diagram of the present device for detectingchemical species;

FIG. 2 shows qualitatively a principle diagram of operation of thepresent detection device;

FIGS. 3A and 3B are schematic cross-sectional views of embodiments ofthe present detection device;

FIG. 4 shows qualitatively the plots of the absorption cross-sectionsfor nitrogen monoxide NO and nitrogen dioxide NO₂, expressed in x10⁻¹⁹cm² and as a function of the wavelength (λ);

FIG. 5 shows a block diagram of an embodiment of a first optoelectronicsensor and a second optoelectronic sensor that form the presentdetection device;

FIG. 6 is a schematic top plan view of an embodiment of the presentdetection device;

FIG. 7 is a schematic cross-sectional view of the embodiment representedin FIG. 6, taken along a line of section VII-VII shown in FIG. 6;

FIG. 8 shows the plot of the absorption of radiation having a wavelengthalternatively equal to 230 nm, 250 nm, 300 nm, and 350 nm within asilicon-carbide junction of the 4H type, as a function of the thicknessof the epilayer (on the hypothesis of fully depleted epilayer);

FIG. 9 is a schematic cross-sectional view of a further embodiment ofthe present detection device; and

FIGS. 10-20 are schematic cross-sectional views of embodiments of thepresent detection device, during successive steps of a manufacturingmethod.

DETAILED DESCRIPTION

FIG. 1 shows a device for detecting chemical species 1, which will bereferred to hereinafter, for brevity, as “detection device 1”.

The detection device 1 comprises a first optoelectronic sensor 2 and asecond optoelectronic sensor 4, and a power supply 6, which is designedto bias the first and second optoelectronic sensors 2, 4, to which it iselectrically connected. Furthermore, the detection device 1 comprises afirst amplifier 8 and a second amplifier 10, for example of thetransimpedence type, and a processing unit 12.

The detection device 1 likewise comprises, as illustrated in FIG. 2 anddescribed in greater detail hereinafter, an optical source 20 designedto generate radiation that impinges, in use, upon the first and secondoptoelectronic sensors 2, 4. Furthermore, in use, a fluid F is arrangedbetween the optical source 20 and the first and second optoelectronicsensors 2, 4, so that the radiation generated by the optical source 20traverses the fluid F before impinging upon the first and secondoptoelectronic sensors 2, 4. In turn, the first and secondoptoelectronic sensors 2, 4 generate a first electrical signal and asecond electrical signal, which will be referred to as “first and seconddetection signals”. The first and second detection signals are supplied,respectively, to the first and second amplifiers 8, 10 and indicate theintensity of the radiation that impinges, respectively, upon the firstand second optoelectronic sensors 2, 4. In turn, the first and secondamplifiers 8, 10 generate, on the basis of the first and seconddetection signals, a first further signal and a second further signal,which will be referred to hereinafter as “first and second processablesignals”. These first and second processable signals are supplied to theprocessing unit 12, which executes the processing operations describedin what follows.

As illustrated in greater detail in FIG. 3A, the detection device 1comprises a chamber 22, which enables functional coupling of the opticalsource 20, the first and second optoelectronic sensors 2, 4, and thefluid F. In particular, the chamber 22 has a fluid inlet IN and a fluidoutlet OUT, by which the fluid F can, respectively, enter and exit fromthe chamber 22. Furthermore, the optical source 20 is arranged at afirst end of the chamber 22, whereas the first and second optoelectronicsensors 2, 4 are arranged at a second end of the chamber 22. In thisway, the radiation generated by the optical source 20 traverses aportion of the chamber 22, and thus passes through the fluid F, beforeimpinging upon the first and second optoelectronic sensors 2, 4.

However possible are variants in which the optical coupling between theoptical source 20 and the first and second optoelectronic sensors 2, 4is obtained in a different way and/or the chamber 22 has a differentshape. Purely by way of example, it is for instance possible that, asillustrated in FIG. 3B, the chamber 22 is formed by a sphericalcontainer 24, which, in addition to forming the fluid inlet IN and thefluid outlet OUT, has an inner wall 25 having a substantially sphericalshape (but for the fluid inlet and outlet) and is designed to reflectthe radiation generated by the optical source 20. More in particular,the first and second optoelectronic sensors 2, 4 and the optical source20 are arranged within the chamber 22, together with a screen 26 of areflecting type. In addition, the screen 26 is arranged between theoptical source 20 and the first and second optoelectronic sensors 2, 4so that the radiation generated by the optical source 26 may not impingeupon the first and second optoelectronic sensors 2, 4, other than afterbeing reflected at least once by the inner wall 25. In this way, thelength of the optical paths that connect the optical source 20 to thefirst and second optoelectronic sensors 2, 4 is increased, given thesame overall dimensions of the chamber 22.

This being said, in what follows reference will be made, without thisimplying any loss of generality, to the case where the detection device1 is designed to detect individually nitrogen monoxide NO and nitrogendioxide NO₂, i.e., to determine the individual concentrations ofnitrogen monoxide NO and nitrogen dioxide NO₂ present in the fluid F. Inthis connection, FIG. 4 shows the plots of the absorption cross-sectionsfor nitrogen monoxide NO and nitrogen dioxide NO₂, expressed in ×10⁻¹⁹cm² and as a function of the wavelength (λ). In this case, without thisimplying any loss of generality, the optical source 20 emits UVradiation. For instance, without this implying any loss of generality,it is assumed that this radiation has a constant spectrum in the range200-400 nm. For practical purposes, the optical source 20 may be formedby a voltaic-arc lamp, or else by a LED or laser diode.

It is likewise assumed, without this implying any loss of generality,that the first and second optoelectronic sensors 2, 4 are semiconductorsensors at least in part of silicon carbide, as described hereinafter.Furthermore, it is assumed that the first optoelectronic sensor 2 issensitive to radiation having a wavelength comprised in a first range of200-230 nm, designated by A in FIG. 4; it is further assumed that thesecond optoelectronic sensor 4 is sensitive to radiation having awavelength comprised in a second range of 230-400 nm. In practice, it isknown that nitrogen monoxide NO absorbs below 230 nm, and thus in therange 200-230 nm, as it is likewise known that nitrogen dioxide NO₂absorbs up to 650 nm, and thus in the entire range between 200 nm and400 nm. The first and second optoelectronic sensors 2, 4 havesensitivity bands that are thus a function of the spectra of absorptionof nitrogen monoxide NO and nitrogen dioxide NO₂. Further, the first andsecond optoelectronic sensors 2, 4 are substantially insensitive toradiation having a wavelength, respectively, falling outside the firstand second ranges.

For practical purposes, the intensity of the radiation that impingesupon the first and second optoelectronic sensors 2, 4, after havingtraversed the fluid F, may be determined on the basis of the so-calledLambert-Beer law. In particular, on the hypothesis of having amonochromatic radiation and an fluidic absorber formed by just one typeof chemical species and with a concentration equal to C, theLambert-Beer law envisages that

I(λ,x)=I ₀(λ)·e ^(−x·σ(λ)X)

where I₀(λ) is the intensity of the monochromatic radiation thatimpinges upon the absorber, and σ(λ) is the absorption cross-section forthe chemical species at the wavelength of the monochromatic radiation;further, I(λ, x) is the intensity of the radiation after it has coveredan optical path of length x within the absorber. Consequently, knowledgeof the intensities I₀(λ) and I(λ, x), of the distance x, and of theabsorption cross-section σ(λ) enables determination of the concentrationC, which is assumed as being constant for the distance x.

In greater detail, in what follows it is assumed that the optical source20 is at a distance x both from the first optoelectronic sensor 2 andfrom the second optoelectronic sensor 4. More in particular, it isassumed that the first and second optical paths that connect the opticalsource 20 to the first and second optoelectronic sensors 2, 4respectively, both have a length x and extend, in use, entirely throughthe fluid F. Furthermore, it is assumed that the absorption of radiationgenerated by the optical source 20 in the range 200-400 nm by chemicalspecies different from nitrogen monoxide NO and nitrogen dioxide NO₂(for example, sulphur dioxide SO₂) is negligible. In addition, in whatfollows the portion of the radiation generated by the optical source 20in the range 200-230 nm and incident, in the absence of the fluid F,upon the first optoelectronic sensor 2 will be referred to as “firstdetection beam”. Instead, the portion of the radiation generated by theoptical source 20 in the range 230-400 nm and incident, in the absenceof the fluid F, upon the second optoelectronic sensor 4 will be referredto as “second detection beam”.

This being said, the first optoelectronic sensor 2 detects the portionof the first detection beam not absorbed either by nitrogen monoxide NOor by nitrogen dioxide NO₂, which depends upon the concentrations andupon the absorption cross-sections of these two chemical species. Inaddition, the second optoelectronic sensor 4 detects the portion of thesecond detection beam not absorbed by nitrogen dioxide NO₂, whichdepends upon the concentration and upon the absorption cross-section fornitrogen dioxide NO₂. The first and second detection signals, which areformed by photocurrents, thus indicate, respectively, i) the combinationof the concentrations of nitrogen monoxide NO and nitrogen dioxide NO₂,and ii) the concentration of nitrogen dioxide NO₂.

In greater detail, with reference to the intensity of the radiation thatimpinges upon the first optoelectronic sensor 2, this is equal to

I ₁ =I ₁₀ ·∫e ^(−x·[σ1(λ)·C1+σ2(λ)·C2]) dλ

where I₁₀ is the (known) intensity of the aforementioned first detectionbeam, σ1 (λ) is the absorption cross-section for nitrogen monoxide NO,σ2(λ) is the absorption cross-section for nitrogen dioxide NO₂, and C1and C2 are, respectively, the concentrations of nitrogen monoxide NO andnitrogen dioxide NO₂ in the fluid F. Consequently, the first detectionsignal and the first processable signal, which are proportional to theintensity I₁, are a function of the concentrations of nitrogen monoxideNO and nitrogen dioxide NO₂.

With reference to the intensity of the radiation that impinges upon thesecond optoelectronic sensor 4, this is equal to

I ₂ =I ₂₀ ·∫e ^(−x·[σ3(λ)·C2]) dλ

where I₂₀ is the (known) intensity of the aforementioned seconddetection beam, and σ3(λ) is the absorption cross-section for nitrogendioxide NO₂. Consequently, the second detection signal and the secondprocessable signal, which are proportional to the intensity I₂, are afunction of the concentration of nitrogen dioxide NO₂.

On the basis of the first and of the second processable signal, theprocessing unit 12 is thus able to determine each one between theconcentration of nitrogen monoxide NO and the concentration of nitrogendioxide NO₂. Without this implying any loss of generality, it is assumedthat the above two concentrations are constant along the optical pathscovered by the first and second detection beams.

In greater detail, in a per se known manner, the processing unit 12numerically determines the concentration C2 of nitrogen dioxide NO₂, onthe basis of a measurement of the intensity 12, as determined by theprocessing unit 12 itself on the basis of the second processable signal.Next, the processing unit 12 numerically determines the concentration C1of nitrogen monoxide NO, on the basis of the concentration C2 ofnitrogen dioxide NO₂ and of a measurement of the intensity I₁, asdetermined by the processing unit 12 itself on the basis of the firstprocessable signal. More precisely, the processing unit 12 determinesestimates of the aforementioned concentrations C1 and C2.

Purely by way of example, in the numerical processing, the processingunit 12 may be based upon the use of the following approximaterelations:

I ₁ =I ₁₀ ·e ^(−x·[σ1m·C1+σ2m·C2]PS)

I ₂ =I ₂₀ ·e ^(−x·σ3m·C2)

where σ1m is the integral of the absorption cross-section for nitrogenmonoxide NO in the range 200-230 nm, σ2m is the integral of theabsorption cross-section for nitrogen dioxide NO₂ in the range 200-230nm, and σ3m is the integral of the absorption cross-section for nitrogendioxide NO₂ in the range 230-400 nm.

As illustrated qualitatively in FIG. 5, the first optoelectronic sensor2 may be formed by a first wide-band sensor 30 a, having a band at leastequal to 200-400 nm, and by a first optical filter 32 a, having apassband of 200-230 nm and arranged over the first wide-band sensor 30a. The first optical filter 32 a may be formed in a per se known mannerby a plurality of dielectric layers; further, the first optical filter32 a may be integrated with the first wide-band sensor 30 a, or else maybe physically separate from the latter. Likewise, the secondoptoelectronic sensor 4 may be formed by a second wide-band sensor 30 b,having a band at least equal to 200-400 nm, and by a second opticalfilter 32 a, having a passband of 230-400 nm and arranged over thesecond wide-band sensor 30 b. The second optical filter 32 b may beformed in a per se known manner by a plurality of dielectric layers;further, the second optical filter 32 b may be integrated with thesecond wide-band sensor 30 b, or else may be physically separate fromthe latter.

According to the embodiment illustrated in FIGS. 6 and 7, the first andsecond optoelectronic sensors 2, 4 are integrated with one another andform a semiconductor device of a monolithic type.

In detail, the detection device 1 comprises a semiconductor body 40 ofsilicon carbide SiC of the 4H type, which in turn comprises a substrate42 and an epitaxial layer 44, formed on the substrate 42.

In greater detail, the substrate 42 is of an N type (for example, dopedwith nitrogen), has a thickness of, for example, 350 μm and has a dopinglevel of, for example, 10¹⁹ cm⁻³. The epitaxial layer 44 is of N-type(for example, doped with nitrogen) and has a doping level of, forexample, 10¹⁴ cm⁻³. Further, the epitaxial layer 44 includes a firstepitaxial region 45 and a second epitaxial region 46, arranged alongsideone another, the first epitaxial region 45 having a thickness comprised,for example, in the range 0.3-0.5 μm, and the second epitaxial region 46having a thickness comprised, for example, in the range 4-6 μm. Thefirst and second epitaxial regions 45, 46 are delimited at the top by afirst top surface S_(a1) and a second top surface S_(a2), respectively,whereas the substrate 42 is delimited at the bottom by a bottom surfaceS_(b).

The semiconductor body 40 further comprises a first anode region 48 anda second anode region 50, of a P+ type (for example, doped withaluminium) and with peak doping level of approximately 10¹⁸ cm⁻³. Morein particular, the first anode region 48 extends within the firstepitaxial region 45, starting from the first top surface S_(a1) and witha thickness comprised, for example, in the range 0.1-0.2 μm.Furthermore, the second anode region 50 extends within the secondepitaxial region 46, starting from the second top surface S_(a2) andwith a thickness comprised, for example, in the range 0.1-0.2 μm.Consequently, the first and second anode regions 48, 50 overlie,respectively, a portion of the first epitaxial region 45 and a portionof the second epitaxial region 46, which have thicknesses, respectively,comprised, for example, in the ranges 0.1-0.4 μm and 3.8-5.9 μm.

The first anode region 48 and the first epitaxial region 45 form thefirst optoelectronic sensor 2, and in particular form a first PNjunction, where the so-called “epilayer”, formed by the portion of thefirst epitaxial region 45 underlying the first anode region 48, has athickness comprised in the range 0.1-0.4 μm. This first PN junction isthus rather shallow and is arranged in the proximity of the first topsurface S_(a1). This implies, as illustrated in FIG. 8, thatsubstantially all the radiation that traverses the first PN junction andhas a wavelength shorter than 230 nm is absorbed by the junction itself.

The second anode region 50 and the second epitaxial region 46 form thesecond optoelectronic sensor 4, and in particular form a second PNjunction, where the so-called “epilayer” has a large thickness.Furthermore, present on a first portion of the second anode region 50 isan absorption layer 59, for example, of polysilicon and having thefunction of absorbing radiation having a wavelength shorter than 230 nm,before it impinges upon the second PN junction. For instance, theabsorption layer 59 may have a thickness comprised in the range 10-50nm.

The detection device 1 likewise comprises a first anode metallization 60and a second anode metallization 62, which are, for example, of titaniumand an AlSiCu alloy (for simplicity of exposition, the distinctionbetween titanium and AlSiCu alloy is not illustrated in FIG. 7).Furthermore, the first and second anode metallizations 60, 62 arearranged, respectively, on the first and second anode regions 48, 50,with which they are, respectively, in direct contact. In particular,without this implying any loss of generality, the second anodemetallization 62 extends over a second portion of the second anoderegion 50 so as to be laterally staggered with respect to the absorptionlayer 59. Further, the first anode metallization 60 extends over a sideportion of the first anode region 48.

The detection device 1 further comprises a layer 66, which will bereferred to hereinafter as “contact layer 66”. The contact layer 66 isarranged underneath the bottom surface S_(b) and is, for example, ofnickel silicide Ni₂Si; purely by way of example, the contact layer 66may have a thickness of, for example, 40 nm. Furthermore, the detectiondevice 1 comprises a cathode metallization 68, arranged underneath thecontact layer 66 and formed for example by a multilayer structureincluding layers (not illustrated individually) formed by titanium,nickel, and gold.

In practice, the first and second epitaxial regions 45, 46 formcorresponding cathode regions. Furthermore, the low doping level of theepitaxial layer 44 causes, even in the absence of biasing, completedepletion both of the portion of the first epitaxial region 45 overlaidby the first anode region 48 and of the portion of the second epitaxialregion 46 overlaid by the second anode region 50. Furthermore, both thefirst and the second optoelectronic sensors 2, 4 can be biasedsimultaneously through the cathode metallization 68, while the first andsecond detection signals generated by them can be acquired,respectively, at the first and second anode metallizations 60, 62.

According to a different embodiment (illustrated in FIG. 9), each one ofthe first and second optoelectronic sensors 2, 4 includes a Schottkyjunction, as well as a PN junction.

In detail, the detection device 1 comprises, instead of the first andsecond anode regions 48, 50, a first metal region 70 and a second metalregion 72, which extend, respectively, on the first and second topsurfaces S_(a1), S_(a2) so as to contact directly the first and secondepitaxial regions 45, 46, respectively. In this case, the first andsecond epitaxial regions 45, 46 have thicknesses, respectively,comprised, for example, in the ranges 0.1-0.4 μm and 3.8-5.9 μm. Thefirst and second anode metallizations 60, 62 contact, respectively, thefirst and second metal regions 70, 72. Further, the second metal region72 is overlaid by the absorption layer 59.

Without this implying any loss of generality, in what follows a methodis described for manufacturing the embodiment illustrated in FIG. 7.

Initially, as illustrated in FIG. 10, the semiconductor body 40 made upof the substrate 42 and the epitaxial layer 44 is formed. Furthermore,formed on the epitaxial layer 44 is a first layer of TEOS oxide 80having a thickness of, for example, 20 μm (FIG. 10, as on the other handalso the subsequent figures, as well as FIGS. 6, 7 and 9 are not inscale). Then, formed underneath the substrate 42 is the contact layer66, for example by sputtering and subsequent annealing, the latter beingcarried out, for example, at 1000° C., in the presence of nitrogen N₂,and having a duration of one minute.

Next, as illustrated in FIG. 11, provided on the first layer of TEOSoxide is a first mask 82, for example a resist mask.

Then, as illustrated in FIG. 12, a process of photolithography iscarried out in order to remove a portion of the first layer of TEOSoxide 80 so as to expose a part of the epitaxial layer 44. Then, thefirst mask 82 is removed.

Next, as illustrated in FIG. 13, a process of reactive ion etching (RIE)is carried out so as to form the first and second epitaxial regions 45,46, as well as the first and second top surfaces S_(a1), S_(a2). Inparticular, a top portion of the exposed part of the epitaxial layer 44is selectively removed in order to form the first epitaxial region 45.Then, the residual portion of the first layer of TEOS oxide 80 isremoved.

Next, as illustrated in FIG. 14, formed on the first and second topsurfaces S_(a1), S_(a2) is a second layer of TEOS oxide 84, which has athickness comprised, for example, between 50 nm and 100 nm.

Then, as illustrated in FIG. 15, by a process of photolithography and asubsequent ion-implantation of dopant species of a P type, a first thinlayer 48′ and a second thin layer 50′ are formed, which extend,respectively, in the first and second epitaxial regions 45, 46, startingfrom the first top surface S_(a1) and the second top surface S_(a2),respectively. In addition, the first and second thin layers 48′, 50′ areto form, respectively, the first and second anode regions 48, 50, oncethe appropriate thermal treatments are terminated, as explainedhereinafter.

In greater detail, the aforementioned step of ion implantation,indicated by the arrows 90, may comprise a plurality of high-dosageimplants (5·10¹⁴−3·10¹⁵ cm⁻²) and increasing energy (for example, in therange 50-200 keV), at a temperature of 400° C., and envisages the use ofa second resist mask 92 for reducing the contamination of sites externalto the regions in which the implantation itself is to be carried out.

Next, as illustrated in FIG. 16, the second mask 92 is removed, forexample by a further wet etch, and annealing is carried out, whichenables formation of the first and second anode regions 48, 50,respectively, starting from the first and second thin layers 48′, 50′.

Next, as illustrated in FIG. 17, the second layer of TEOS oxide 84 isremoved. Furthermore, deposited on the first and second top surfacesS_(a1), S_(a2) is a polysilicon layer 100 having, for example, athickness comprised in the range 10-50 nm. Provided on the polysiliconlayer 100 is a third mask 102.

Next, as illustrated in FIG. 18, a further process of photolithographyis carried out in order to remove selectively portions of thepolysilicon layer 100, for example by a wet etch so as to form theabsorption layer 59. Then, the third mask 102 is removed.

Next, as illustrated in FIG. 18, formed on the first and second topsurfaces S_(a1), S_(a2), as well as on the absorption layer 59, is abarrier layer 110, for instance, of titanium and having a thickness of,for example, 100 nm. In addition, formed on the barrier layer 110 is afunctional layer 112 of a metal type, for example, of the AlSiCu alloy.Both the barrier layer 110 and the functional layer 112 may be obtainedby sputtering.

Next, as illustrated in FIG. 19, portions of the barrier layer 110 andof the functional layer 112 are selectively removed, for example by awet etch, so as to form the first and second anode metallizations 60,62.

Finally, in a way not illustrated, the cathode metallization 68 isformed, for example by sputtering, underneath the contact layer 66.

In the case where, instead, an embodiment is adopted in which the firstand second optoelectronic sensors form respective Schottky junctions,this may be obtained by carrying out the operations illustrated in FIGS.10-13. Next, as illustrated in FIG. 20, a metal layer 130 is formed onthe first and second epitaxial regions 45, 46, which is then patterned,by selective removal of portions, so as to form the first and secondmetal regions 70, 72. The absorption layer 59 and the first and secondanode metallizations 60, 62 are then formed as described previously, buton the first and second metal regions 70, 72.

From what has been described and illustrated previously, the advantagesthat the present solution affords emerge clearly.

In particular, the present detection device enables simultaneousdetection of the concentrations of two different chemical species, witha high sensitivity.

For this purpose, the first and second optoelectronic sensors areilluminated simultaneously by the optical source.

Furthermore, in the case where the first and second optoelectronicsensors are of silicon carbide, the sensitivity is kept high also athigh temperature, thanks to the low leakage currents in the siliconcarbide. Further, both the first optoelectronic sensor and the secondoptoelectronic sensor may be reverse biased with very low voltages (inmodulus), possibly even in the photovoltaic regime. In addition, thefirst and second optoelectronic sensors can operate also in the presenceof chemical agents and have characteristics that remain very stable overtime.

Furthermore, in the case where the first and second optoelectronicsensors are integrated with one another, the detection device has verysmall overall dimensions. Again, the detection device may readily beadapted to different pairs of chemical species by varying the thicknessand the material of the epitaxial layer accordingly. In addition, thedetection device may be used not only in the presence of a flow offluid, but also in the presence of a fluid substantially at rest, oreven in the presence of a solid containing the chemical species to bedetected.

In conclusion, it is clear that modifications and variations may be madeto what has been described and illustrated herein, without therebydeparting from the scope of the present disclosure.

As mentioned previously, the first and second optoelectronic sensors maybe sensors of a different type, such as for example vacuumphotomultiplier tubes (PMTs). Furthermore, in the case where the firstand second sensors are again semiconductor sensors integrated together,the semiconductor body may be formed by a semiconductor materialdifferent from silicon carbide, such as for example silicon, or elsegallium nitride GaN or aluminium gallium nitride AlGaN.

In addition, the first and the second sensitivity bands, whichcorrespond, respectively, to the first and second optoelectronicsensors, may be separate from one another. It is likewise possible forthe first and second sensitivity bands to be instead partiallyoverlapping in an intersection range. In this case, it is possible, butnot necessary, for the absorption cross-section for at least one of thefirst and second chemical species to be zero within the intersectionrange. In general, even though the fact that the absorptioncross-section for a chemical species is zero in the second absorptionband simplifies the operations performed by the processing unit 12, itis in any case possible that in each one of the first and secondsensitivity bands the absorption cross-sections for both of the chemicalspecies to be detected are at least locally (i.e., in a portion of thesensitivity range) nonzero. In this case, with reference, for example,once again to nitrogen monoxide NO and nitrogen dioxide NO₂, theintensity of the radiation that impinges upon the second optoelectronicsensor is equal to

I ₂ =I ₂₀ ·∫e ^(−x·[σ4(λ)·C1+σ3(λ)·C2]) dλ

where σ4(λ) is the absorption cross-section for nitrogen oxide NO. Thelatter relation may be approximated as:

I ₂ =I ₂₀ ·e ^(−x·[σ4m·C1+σ3m·C2])

where σ4m is the integral of the absorption cross-section for nitrogenoxide NO in the second sensitivity band. The processing unit 12 can thusdetermine the concentrations C1 and C2 by solving a system of twoequations with two unknowns, on the basis of the intensities I₁ and I₂.

In general, it is further possible for the optical source to have anon-constant spectrum, in which case the numeric processing operationexecuted by the processing unit 12 is modified in a per se known manner.

As regards the processing unit 12, this may be integrated in thesemiconductor body 40, and thus may be integrated with the first andsecond optoelectronic sensors 2, 4, or else may be external to thelatter.

As regards the first and second anode regions, when these are arrangedon the first and second top surfaces S_(a1), S_(a2), they may be formedby a non-metal conductive material, such as for example polysilicon.Consequently, the first and second metal regions 70, 72 may be replacedby corresponding non-metal conductive regions, for instance ofpolysilicon. In this case, during manufacture, a correspondingconductive layer is formed, instead of the metal layer 130.

As regards the absorption layer 59, this may be of a material differentfrom polysilicon, such as silicone, or else an optically absorbent metalmaterial, such as titanium nitride TiN.

Finally, all the types of doping may be reversed with respect to whathas been described.

The various embodiments described above can be combined to providefurther embodiments. These and other changes can be made to theembodiments in light of the above-detailed description. In general, inthe following claims, the terms used should not be construed to limitthe claims to the specific embodiments disclosed in the specificationand the claims, but should be construed to include all possibleembodiments along with the full scope of equivalents to which suchclaims are entitled. Accordingly, the claims are not limited by thedisclosure.

1. A device, comprising: a substrate with a first surface and a secondsurface facing away from the first surface; an epitaxial layer on thefirst surface of the substrate, the epitaxial layer having plurality ofedges, a third surface with a first perimeter, and a fourth surface witha second perimeter, the third surface is closer to the first surface ofthe substrate than the fourth surface; a first anode region on the thirdsurface of the epitaxial layer and positioned within the firstperimeter, the first anode region spaced from the plurality of edges ofthe epitaxial layer; a second anode region on the fourth surface of theepitaxial layer and positioned within second perimeter, the second anoderegion spaced from the plurality of edges of the epitaxial layer; afirst anode metallization on the first anode region; and a second anodemetallization on the second anode region.
 2. The device of claim 1,further comprising a contact layer on the second surface of thesubstrate.
 3. The device of claim 2, further comprising a cathode layeron the contact layer.
 4. The device of claim 1, wherein the epitaxiallayer further comprises a wall extending from the third surface to thefourth surface, the wall positioned between the first anode region andthe second anode region.
 5. The device of claim 4, wherein: the firstperimeter includes a plurality of first sides aligned with respectiveedges of the plurality of edges and a second side aligned with the wall;and the second perimeter includes a plurality of first sides alignedwith respective edges of the plurality of edges and a second sidealigned with the wall.
 6. The device of claim 1, further comprises anabsorption layer on the second anode region.
 7. The device of claim 1,wherein: the first anode metallization is positioned adjacent to acenter of an edge of the first anode region; and the second anodemetallization is positioned adjacent to a center of an edge of thesecond anode region.
 8. A device, comprising: a substrate with a firstsurface and a second surface facing away from the first surface; anepitaxial layer on the first surface of the substrate, the epitaxiallayer having a third surface, a fourth surface, and fifth surface, thethird surface and the fourth surface face away from the first surface ofthe substrate, the fifth surface of the epitaxial layer extends from thethird surface to the fourth surface and extends from the third surfaceto the fourth surface; a first optoelectronic sensor on the thirdsurface of the epitaxial layer; and a second optoelectronic sensor onthe fourth surface of the epitaxial layer.
 9. The device of claim 8,wherein the fifth surface is positioned between the first optoelectronicsensor and the second optoelectronic sensor.
 10. The device of claim 8,wherein the fifth surface separates the third surface from the fourthsurface.
 11. The device of claim 8, further comprising: a contact layeron the second surface of the substrate; and a cathode metallizationlayer on the contact layer, the cathode metallization layer iselectrically coupled to the first anode region and the second anoderegion.
 12. The device of claim 8, wherein the first optoelectronicsensor further comprises: an anode region on the third surface of theepitaxial layer; and an anode metallization on the anode region.
 13. Thedevice of claim 12, wherein the anode metallization on the anode regionis positioned adjacent to a center of an edge of the anode region. 14.The device of claim 8, wherein the second optoelectronic sensor furthercomprises: an anode region on the fourth surface of the epitaxial layer;an anode metallization on the anode region; and an absorption layer onthe anode region that abuts the anode metallization.
 15. The device ofclaim 14, wherein the anode metallization on the anode region ispositioned adjacent to a center of an edge of the anode region.
 16. Amethod, comprising: forming an epitaxial layer with a first portion witha first thickness and a second portion with a second thickness greaterthan the first thickness on a first surface of a substrate; forming acontact layer on a second surface of the substrate facing away from thefirst surface of the substrate; forming a first anode region on thefirst portion of the epitaxial layer and a second anode region on thesecond portion of the epitaxial layer; forming a first anodemetallization on the first anode region and a second anode metallizationon the second anode region; and forming a cathode layer on the contactlayer.
 17. The method of claim 15, wherein forming the epitaxial layerwith the first portion with the first thickness and the second portionwith the second thickness further comprises: forming an oxide layer onthe epitaxial layer; forming a mask layer on the oxide layer; removing aportion of the oxide layer from a location on the epitaxial layer;etching the epitaxial layer at the location forming the first portion ofthe epitaxial layer with the first thickness, the second portion withthe second thickness, and a wall that extends from a surface of thefirst portion to a surface of the second portion; and removing the masklayer and the oxide layer aligned with the second portion of theepitaxial layer.
 18. The method of claim 15, wherein forming the firstanode region and the second anode region further comprises: forming anoxide layer on the first portion of the first epitaxial layer and thesecond portion of the second epitaxial layer; forming a mask layer onthe oxide layer; removing portions of the mask layer to expose portionof the oxide layer; exposing the exposed portions of the oxide layer toions; and removing the mask layer and the oxide layer.
 19. The method ofclaim 15, further comprising forming an absorption layer on the secondanode region including: forming a polysilicon layer on the first portionand the second portion of the epitaxial layer; forming a mask layer onthe polysilicon layer, the mask layer is aligned with the second anoderegion; etching the polysilicon layer forming the absorption layer onthe second anode region, the absorption layer covering a first portionof the second anode region and exposing a second portion of the secondanode region; and removing the mask layer.
 20. The method of claim 19,wherein forming the second metallization on the second anode regionfurther comprises: forming the second metallization on the secondportion of the second anode region that is exposed.